Photographic developing compositions



United States Patent 3,265,499 PHOTOGRAPHIC DEVELOPING COMPOSITIONSJozef Frans Willems, Wilrijk-Antwerp, and Georges Frans van Veelen,Mortsel-Antwerp, Belgium, assignors to Gevaert Photo-Producten N.V.,Mortsel, Belgium, a company of Belgium No Drawing. Filed July 9, 1962,Ser. No. 208,572 Claims priority, application Great Britain, July 10,1961,

9 Claims. (CI. 96-29) This invention relates to the development ofphotographic materials, containing exposed silver halide, to newdeveloping combinations, photographic materials and solutions containingsuch combinations.

It is known that certain developer solutions containing severaldeveloping substances in concentrations equal to that of the separatedeveloper solutions of each of these substances, show a higher additivedeveloping activity than the awaited one. This phenomenon is called thesuperadditive development.

An example of this superadditive development is obtained with thecombination of p-monomethylaminophenol hemisulphate and hydroquinonewhich has been described by G. Pizzighelli, Leitfaden der praktischenPhotographic, Auflage 14 (Paul Hanneke), p.177.

Now it has been found that an exceptional super-additive developingactivity appears, exceeding that of the mixture ofp-monomethylaminophenol hemisulphate and hydroquinone when using in thedevelopment of an exposed silver halide emulsion layer a combination ofdeveloping agents comprising hydroquinone and a p-aminophenol derivativecorresponding to one of the following general formulae:

R represents a member selected from the group consisting of a hydrogenatom, an alkyl radical such as methyl, ethyl, propyl, butyl, pentyl andhexyl, a substituted alkyl radical such as hydroxy methyl,fi-hydroxyethyl, v'y-hydroxypropyl, fi-hydroxybutyl, fi-carboxybutyl,e-ClFbOXYPflHiYl, w-carboxyhexy-l, fi-sulfobutyl, e-sulfopentyl,w-sulfohexyl, fi-sulfoatobutyl, esuilf oatopen'tyl, w sulfoatohexyl andB- acylamino ethyl, each of X and X represents a member selected fromthe group consisting of a hydrogen atom, a chlorine atom and anelectron-donating group such as an alkyl group, an alkoxy group, anamino group, a monoalkyl amino group, a dialkylamino group, an acylaminogroup and a 'sul-fonamido group, and each of A and A represents a memberselected from the group consisting of an ethylene radical, a propyleneradical, a substituted ethylene radical and a substituted propyleneradical.

More particularly the p-aminophenol derivatives identified hereinafterhave been proved to be very suitable for being applied in the processaccording to the present invention:

( 1 1- (4-hydroxyphenyl) -pyrrolidine (2)1-(3-chloro-4-hydroxyphenyl)-pyrrolidine (3)1-(3,5-dimethy1-4-hydroxyphenyl)-pyrrolidine1-(3-amino-4-hydroxyphenyl)-pyrrolidine (5 1- 3-methoxy-4-hydroxyphenyl)-pyrrolidine (6) 1-(3-methylsulfonamino-4-hydroxyphenyl)-pyrrolidine (7)1- 3 -acetylamino-4-hydroxyphenyl -pyrrolidine (8) 6-hydroxy- 1 ,2,3,4-tetrahydroquinoline (9) l-ethyl-6-hydroxy-l,2,3,4-tetrahydroquinoline(10) 1-(methylsulfonylamino-ethyl)-6-hydroxy-1,2,3 ,4-

tetrahydroquinoline (1 1 1- (Z-hydroxyethyl)-6-hydroxy-1,2,3,4-tetrahydroquinoline (12) 1-(4-sulfobutyl)-6-hydroxy-1,2,3,4-tetrahydroquinoline.

The following are preparations of some p-aminophenol derivatives used inthis invention.

PREPARATION 1 1e(4-hydroxyphenyl-pyrrolidine hydrochloride is preparedas follows:

44 g. (0.25 mol) of l-(p-methoxyphenyl)-pyrrolidine and 200 cm. of a 48%solution of hydrobromic acid are refluxed for 8 hours. The reactionmixture is evaporated and the residue is dissolved in 300 cm. of water.Then it is neutralized with sodium bicarbonate. The precipitate issucked off and recrystallized from a mixture of dioxan and water (1:2).Melting point: 147 C.

The free base is dissolved in 1000 cm. of ether and hydrogen chloride ispassed through the solution. The obtained precipitate is sucked ofi,washed with ether and dried. Melting point: 130 C.

PREPARATION 2 1 (3-chloro-4-hydroxyphenyl)-pyrrolidine is prepared asfollows:

To a mixture of 14.35 g. of 2-chloro-4-amir1ophenol, dissolved in cm. ofethanol and 13.8 g. of potassium carbonate, 21.6 g. of 1,4-dibromobutaneare dropwise added while stirring and introducing nitrogen. The mixtureis refluxed .for 8 hours. Then the solid substance is filtered whilebeing warm, twice extracted with boiling ethanol and once again'filtered01f. Both filtrates are evaporated and the resulting viscous mass istreated with sodium hydroxide. The obtained solution is neutralized withhydrochloric acid which gives a precipitate that is separated. Theprecipitate is recrystallized from ethanol/ water (1:1). Melting point:114116 C.

PERPARATION 3 1-(3,5-dimethyl-4-hydroxyphenyl)-pyrrolidine is preparedas follows:

8 g. of 2,6-dimethyl-4-aminophenol, 12.5 g. of 1,4-dibromobutane, 8 g.of potassium carbonate and 100 cm. of absolute ethanol are refluxed for10 hrs. The solid substance is filtered off while being warm, twiceextracted with boiling ethanol and once again filtered off. Thefiltrates are evaporated and the residue is treated with ether. Theether extract is evaporated and the residue is recrystallized from ethylacetate. The filtrate of this recrystallization is evaporated and theresidue recrystallized from water/ethanol. Melting point: 94 C.

PREPARATION 4 1-(3-amino-4-hydroxyphenyl)-pyrrolidine dihydrobrobromideis prepared as follows:

A solution 9 g. of 3-acetylamino-4-methoxyaniline, prepared as describedin J. Am. Chem. Soc. 69 (1947) 586, 6.9 g. of potassium carbonate and10.8 g. of 1,4-dibromobutane in 100 cm. of absolute ethanol is refluxedfor 8 hrs. The formed precipitate is sucked off and treated with boilingethanol. The filtrates are allowed to cool whereby a precipitate isformed which is also sucked off. The remaining filtrate is evaporatedtill the half of its volume and then once again allowed to cool. Theformed precipitate is sucked off and then together with the aboveprecipitate recrystallized from ethanol. Melting point: 170 C.

Then 23.4 g. of the thus obtained 1-(3-acetamino-4-methoxyphenyl)-pyrrolidine is refluxed together with a 48% solutionhydrobromic acid. The reaction mixture is evaporated and the residuetreated with ether. The precipitate is then sucked off and dried.Melting point: 190 C.

PREPARATION 5 1-(3-methoxy-4-hydroxyphenyl)-pyrrolidine is prepared asfollows:

13.9 g. of 2-methoxy-4-aminophenol, 21.6 g. of 1,4- dibromobutane, 13.8g. of potassium carbonate and 120 cm. of absolute ethanol are refluxedfor hrs. While introducing nitrogen. The formed precipitate is filteredoff while being warm and then washed twice with ethanol.

The filtrates are evaporated and the residue extracted with ether. Theether extract is evaporated and the formed oil becomes solid after acertain time. substance is recrystallized from petroleum naphtha(boiling range: 90-120 C.) in the presence of decolourising carbon.Melting point: 72 C.

PREPARATION 6 1-( 3 methylsulfonylamino-4-hydroxyphenyl) pyrrolidine isprepared under an oxygen-free nitrogen atmosphere in a continuous liquidextraction apparatus, using ether as extraction liquid.

From the hydrobromide of 1-(3-amino-4-hydroxyphenyl)-pyrrolidine thebase is set free by adding sodium bicarbonate. This free baseimmediately reacts with the added methane sulfonyl chloride.

The formed 1-(3=methylsul-fonylamino-4-hydroxyphenyl)-pyrrolidine isfinally separated from the ether. Melting point: 180 C.

PREPARATION 7 1-(3-acetylamino-4-hydroxyphenyl)-pyrrolidine is preparedunder an oxygen-free nitrogen atmosphere, in continuous liquidextraction apparatus, using ether as extraction liquid.

From the hydrobromide of 1-(3-amino-4-hydroxyphenyl) pyrrolidine thebase is set free by adding sodium carbonate.

The thus obtained free base immediately reacts with the added aceticacid anhydride.

The formed 1-(3-acetylamino-4-hydroxyphenyl)-pyrrolidine is finallyseparated from the ether. Melting point: 244-246 C. Y

The solid 4 PREPARATION s 6-hydroxy-1,2,3,4-tetrahydroquinoline isprepared according to the method described in the German patentspecification No. 42,871. Melting point: 148 C.

PREPARATION 9 1-ethyl-6-hydroxy-1,2,3,4 tetrahydroquinolinehydrochloride is prepared as follows:

A solution of 37 g. of 6-hydroxy-1,2,3,4-tetrahydroquinoline, 26.2 g. ofethyl bromide and 17.2 g. of potassium carbonate dissolved in 250 cm. ofabsolute ethanol is refluxed for 5 hrs. while stirring. The reactionmixture is cooled till room temperature and the formed potassium bromideis sucked off. The alcoholic solution is acidified with alcoholichydrochloric acid whereby a precipitate is formed, which is sucked offand dried. Melting point: 214 C.

PREPARATION 101-(methylsulfonylarnino-ethyl)-6-hydroxy-1,2,3,4-tetrahydroquinolinehydrochloride is prepared as follows:

7.45 g. of G-hydroxy-1,2,3,4-tetrahydroquinoline, 10.1 g. of1-bromo-2-methylsulfonamide-ethane, 3.45 g. of potassium carbonate and50 cm. of absolute ethanol are refluxed for 10 hrs. While stirring. Thesolution is filtered while being warm and the solid substance is twiceextracted with boiling ethanol. Both filtrates are evaporated till aviscous mass remains and then cm. of N hydrochloric acid are added. Thesolution is heated for 15 min. on a water-bath whereupon it isevaporated. The residue is rescrystallized from ethylene glycolmonomethyl ether. Melting point: 175 C.

PREPARATION 11 1 (2 hydroxyethyl) 6 hydroxy l,2,3,4 tetrahydroquinolinehydrochloride is prepared as follows:

10.5 g. of 6-hydroxy-1,2,3,4-tetrahydroquinoline and 8.75 g. ofbromo-ethanol are heated for 2 hr. on a water bath whilst stirring. Thenthe solid substance is stirred for 15 min. with 50 cm. of a 10% solutionof potassium hydroxide and 5 cm. of benzyl chloride. The reaction-massis then extracted with ether and the ether extract treated with 5 Nhydrochloric acid. The aqueous layer is evaporated and the residueboiled with absolute ethanol. The formed precipitate is filtered off andthe filtrate is allowed to cool. The formed crystals are sucked off anddried. Melting point: 168 C.

PREPARATION 12 1 (4 sulfobutyl) 6 hydroxy 1,2,3,4 tetrahydroquinoline isprepared as follows:

8.1 g. of 6-hydroxy-1,2,3,4-tetrahydroquinoline and 7.3 g. of butanesultone are heated for 2 hr. on a water-bath. A solid substance isformed. Then, heating is continued for another 12 hr. on an oil-bath at150 C. After cooling, the solid substance is mixed with ether whilepulverizing in a mortar and then dried. Melting point: C.

In the preparation of a developing bath or a photographic materialaccording to this invention, the p-aminophenol derivatives used in thisinvention are normally added in the form of their salts (e.g., in theform of their hydrochloride).

From the theoretical point of view it is noteworthy that thesuperadditive effect of a developing combination according to thepresent invention increases with the number and the length of the'alkylgroups on the p-nitrogen atom of the p-aminophenol derivatives accordingto the general formulae. An exceptionally strong increase of thesuperadditive eifect has been observed when using a p-aminophenolderivative according to the above general formulae having a pyrrolidinenucleus in p-position of the hydroxyl group. A same important increaseis observed if a compound is used according to the above generalformulae having fused rings as in 6-hydroxy- 1,2,3,4-tetrahydroquinolineand 9-hydroxyjulolidine.

The strong superadditive effect of these compounds can probably beascribed to the planar structure of their molecules whereby stericalhindering is restricted to a minimum. A possible proof in this directionis the fact that no superadditive effect has been observed if, e.g., thepyrrolidine nucleus is replaced by a non-planar piperidine nucleus.

Besides the devoloping composition of hydroquinone and compoundsaccording to the present invention, the

developing bath can contain the usual ingredients, e.g., buffercompositions which may comprise salts such as carbonates, borates,phosphates, bisulphites, sulphites, metabisulphites and acids such asboric acid and citric acid. Further, the developing bath may containpotassium bromide and water-softening agents such as polyphosphates andderivatives of ethylene diamine tetraacetic acid, antifogging agents andwetting agents as well as other compounds known in the photographicdevelopment technique.

The pH of the baths may vary within wide limits, preferably between 8and 11 so that a quick and hard development or a slow and softdevelopment can be obtained at will.

The ratio of hydroquinone to a p-aminophenol derivative used in thepresent invention can be chosen in such a way that the combination issuited for the development of all kinds of materials including materialshaving little sensitive silver chloride emulsion layers as well as mate-:rials having highly sensitive silver bromo-iodide emulsion layers.

veloping agent described hereinbefore to an amount of 5 g. ofhydroquinone per litre. Of course, larger amounts of said p-aminophenolderivatives can be used, although the superadditive effect obtained withhigher concentrations is not more considerable. Preferably, 50 mg. to 2g. of p-arninophenol derivative and from 5 to 20 g. of hydroquinone perlitre are used.

Combinations of developing agents used in this invention may also beapplied in the baths and/ or in the lightsensitive material and/or inthe image-receiving material used in the application of the silvercomplex diffusion transfer process, the principle of which is describedin the British patent specifications 614,155 and 654,630 and in theGerman patent specification 887,733. For more details concerning thesilver complex diffusion transfer process, the different embodiments ofthe materials and apparatus used therein, there can be referred toProgress in Photography 1955-1958, pp. 2436, and the patent literaturecited therein.

According to a special embodiment both hydroquinone and at least one ofthe p-aminophenol derivatives according to the general formulae areincorporated in the imagereceiving material, preferably in theimage-receiving layer in an amount of preferably 0.2 g. to 20 g. ofhydroquinone and 20 mg. to 2 g. of p-aminophenol derivative per sq. m.

Such an image-receiving material is normally used in that type of silvercomplex diffusion transfer process wherein a processing liquid is usedcomprising an aqueous alkaline solution.

Accordingly, the present invention includes any mate rial in which animage can be formed by diffusion transfer from an image-wise exposedsilver halide emulsion layer according to the silver-salt diffusiontransfer process, said material incorporating development nuclei forpromoting development of diffused silver-salt to metallic silver orincorporating a compound or compounds capable of reacting with anothercompound or compounds to form such nuclei in situ, and the said materialincorporating hydroquinone and at least one compound cor-responding tothe above general formulae. Preferably the image-receiving material alsoincorporates a compound or compounds for complexing or solubilizingsilver halide, e.g., sodium thiosulphate or sodium thiocyanate.

In the silver complex diffusion transfer process, a silver image can beformed on an image-receiving material according to the invention, bypressing it into contact with an image-wise exposed light-sensitivematerial in the presence of a processing liquid comprising an aqueousalkaline solution; neither this solution nor the light-sensitivematerial need contain photographic developers.

Suitable processing liquids for such a process are solutions of basiccompounds, e.g., solutions of sodium hydroxide, potassium hydroxide,lithium hydroxide, sodium carbonate and trisodium phosphate. The amountof dissolved salt required depends on its power to impart alkalinity.For a compound which is weak in this respect, e.g., trisodium phosphate,it is appropriate to use an amount of the anhydrous salt of from 50 to200 g. per liter. In the case of a compound which imparts a high degreeof alkalinity, e.g., sodium hydroxide, an amount of from 5 to 20 g. willsuffice.

Anhydrous sodium sulphite may be incorporated into the processingliquid, e.g., in an amount of from 10 g. to 40 g. per liter.

The processing liquid may further contain other usual ingredients suchas sodium bromide, calcium sequestering compounds and substances whichfavourably influence the image-tone, e.g., 1-phenyl-5-mercaptotetrazoleor similar products, e.g., those described in the British patentspecification 561,875 and the Belgian patent specification 502,525.

The image-receiving material may incorporate further compounds which areuseful ingredients for image-receiving materials to be used in thediffusion transfer process, e.g., sodium sulphite as known per se orpotassium metabisulphite as described and claimed in the French patentspecification 1,296,888.

An image-receiving material according to the invention may, e.g.,consist of a support which is impregnated with development nuclei or asubstance or substances for forming such nuclei in situ. As analternative such nuclei or nuclei-forming substances may be incorporatedin an image-receiving layer applied onto such support. Animage-receiving material according to the invention preferably comprisesa non-light-sensitive colloid layer, e.g.,

a water permeable organic colloid layer, e.g., a gelatin layer, on apaper or other support, the colloid layer incorporating the developmentnuclei or nuclei forming component(s) and the hydroquinone/p-aminophenolderivative developing combination. By way of example an image-receivingmaterial can be manufactured by applying a thin layer on a support froman aqueous suspension containing developing nuclei and comprising perliter of suspension 20 to g. of gelatin, 2 to 50 g. of hydroquinone, 3to 12 g. of p-aminophenol derivative (preferably in salt form) 10 to 60g. of anhydrous sodium thiosulphate, :5 to 40 g. of anhydrous sodiumsulphite and 5 to 40 g. if potassium metabisulphite.

The concentration of alkali in the processing liquid and theconcentration in the image-receiving layer of the products identifiedabove are not critical and other concentrations than those referred tomay be used.

By adding a p-aminophenol derivative as aforesaid to an image-receivinglayer which contains hydroquinone an image-receiving material isobtained which even when used in a diffusion transfer process with alight-sensitive material and a processing liquid neither of whichcontains developer, is found to cause the primary and secondarydevelopment stages to proceed so rapidly, that in the most .moderndeveloping apparatus for quick treatment very good images are obtained.This is surprising, since the primary and secondary development stagescan only start when the image-receiving and light-sensitive materialsare pressed together.

An image-receiving material according to the invention can be used inconjunction with a light-sensitive material having a silverhalideemulsion as known per se or conventionally used in the art of diffusiontransfer. The emulsion composition is not critical, provided its silversalt(s) is (are) capable of development and diffusion in the exposed andnon-exposed areas respectively with the rapidity required in diffusiontransfer processes. Silver chloride emulsions, which may contain silverbromide or silver iodide, and to which other ingredients have been addedso as to impart the desired emulsion characteristics are preferablyused. The emulsion is normally cast in such a way that 0.5 to 2 g. ofsilver are applied per sq. m., of support. Any such emulsion can behardened or slightly hardened.

Development nuclei for silver halide complexes suitable for promotingthe formation of the silver-containing image in the image-receivinglayer are the sulphides of heavy metals, e.g., of antimony, bismuth,cadmium, cobalt, lead, nickel, silver and zinc. Selenides,polysulphides, polyselenides, mercaptanes, stannous halides, heavymetals or their salts and fogged silver halides are also suitable forthis purpose.

The image-receiving layer of an image-receiving material according tothe invention may comprise one or more water-insoluble metal alginatesor a chromium salt of carboxy-methyl cellulose as described and claimedin the Belgian patent specifications Nos. 609,394 and 609,- 395.

According to another special embodiment, the hydroquinone can be presentin the image-receiving material and at least one of the aforesaidp-aminophenol derivatives in the light-sensitive material. Thep-aminophenol derivatives, when incorporated in the light-sensitivematerial, e.g., in the silver halide emulsion layer, or in awater-permeable layer which is in effective contact with said emulsionlayer, cause practically no fog since, in then absence of hydroquinone,they only possess a very weak developing activity. An image-receivingmaterial containing hydroquinone is more particularly described in theFrench patent specification 1,296,888. By an effective contact there ismeant that developing agents can diffuse from said water-permeablelayer, e.g., a nonlight-sensitive colloid layer adjacent to thelight-sensitive emulsion layer to the latter layer.

Lightsensitive silver chloride emulsions, which may also comprise silverbormide and silver iodide, are preferably used. The emulsion isgenerally coated in such a way that 0.5 to 2 g. of silver is present persq. m. and that 12 sq. m. are covered per litre of emulsion.

The emulsion, ready for coating, contains per kg. prefera'bly from 2 tog. of the above p-aminophenol derivative.

In the last embodiment too, a processing liquid comprising an aqueousalkaline solution can be used. The last embodiment is also especiallysuited for rapid processing.

With regard to the combination p-amonomethylaminophenolhemisulphate/hydroquinone the combinations of developers used in thepresent invention show the advantage that by the use of smallerconcentrations an equivalent and mostly a higher developing activity isobtained. The developing compositions according to this invention arenot sensitive to hydrolysis even in strong alkaline solution, whereascompositions with 1-pheny1-3-pyrazolidone hydrolyse in strong alkalinebaths.

The following examples illustrate the present invention.

sensitive silver halide emulsion layer, coated onto a cellulosetriacetate support, are exposed through a grey filter with alight-quantity (E) which corresponds to the shoulder part of thedensity/log E curve.

Each of these film strips are developed at 20 C. in separate developingbaths. One of them is developed in a bath A containing as developingagent only hydroquinone and having the following composition:

Sodium carbonate g 20 Sodium hexametaphosphate g 1 Sodium sulfite g 20Potassium bromide g 0.5 Hydroquinone g 4.4

Water till 1 l.

The other strips are respectively developed in baths, having the samecomposition as bath A but containing moreover an equivalent amount of adeveloping agent as listed in Table I given hereinafter. The densitiesare determined respectively after a developing time of 30, 60, and 120sec.

TABLE I Density (D) Time of development 30 sec. 60 sec. 90 sec. 120 seeBath A 0. 04 0. 04 0. 10 0. 18 Bath A+45 mg. of p-aminophen0l--. 0. 040. 06 0. 12 0.30 Bath A+53 mg. of p-monomethyl aminophenol hemisulphate0.06 0.20 0.75 1. 40 Bath A+60 mg. of 4-(N,N-dimethylaminophenoD-oxalate O. 06 0. 18 0. 74 1. 40 Bath A+66 111g. of4-(N,N-diethylaminophenol)-hemisulphate 0. 06 0.20 0. 76 1. 41 Bath A+61mg. of 1-(4-hydroxyphenyD-pyrrolidine hydrochloride- 0. 11 1. 10 2. 50Bath A+68 mg. of 1-(3-acetylamino- 4-hydroxyphenyl)-pyrrolidine 0.100.73 1. 85 Bath A+66 mg. of 1-(4-hydroxyphenyhpiperidinehydrochloride... 0. 04 0. 04 0. 08 0. 15 Bath A+46 mg. of6-hydroxy-1,2,3,4-

tetrahydroquinoline 0. 18 1. 35 2. 10 Bath A+66 mg. ofl-ethyl-fi-hydroxy-l,2,3,4-tetrahydroquinoline hydrochloride 0. 20 l. 482. 37 Bath A+61 mg. of 1-(3-ehloro-4- hydroxyphenyl)-pyrrolidine 0. 080. 62 1. 75 Bath A+60 mg. of 1-(3-methoxy-4- hydroxyphenyl)-pyrrolidlne0. 23 0.90 1. 52 Bath A+60 mg. of 1-(3,5-dimethyl-4-hydroxyphenyl)-pyrrolidine 0. 12 1.00 2. 10 Bath A+ mg. of 1-(methylsulfonylaminoethyl)-6-hydroxy-1,2,3,4-

tetrahydroquinoline hydrochloride. 0.10 0.99 2.01

Example 2 none and having the following composition:

Boric acid g 5 Borax g 10 Sodium hexametaphosphate g 1 Sodium sulfite gHydroquinone g 4.4

Water up to 1000 cm.

The other strips are respectively developed in baths having the samecomposition as bath B but moreover containing an equivalent amount of adeveloping agent as listed in Table II given hereinafter. The densitiesare determined respectively after a developing time of 2, 4, 6, 8 and 10min.

TABLE II Density (D) Time of development 2 4 g 10 mm. mm. mm. mm. mm.

BathB 0.04 0.04 0.04 0.04 0.04 Bath B+45 mg. of p-aminophenol 0.04 0.040.04 0.04 0.04 Bath B+53 mg. of p-monomethyl aminophenol hemisulphate0.04 0.04 0.10 0.25 0.45 Bath B+60 mg. of4N,N-dimethylaminophenoloxalate 0.04 0.08 0. 22 0.52 0.91 Bath B+66 mg.of 4-N,N-diethylaminophenolhemisulphate 0.04 0.17 0.60 1.13 1.66 BathB+61 mg. of 1-(4-hydroxyphenyl)-pyrrolidine hydr0chlor1de. 0.35 1.432.12

Example 3 Strips of a photographic material comprising a lightsensitivesilver halide emulsion layer, coated onto a cellulose triacetatesupport, are exposed through a grey filter with a light-quantity (E)which corresponds to the shoulder part of the density/ log E curve.

Each of these exposed film strips are developed at 20 C. in separatedeveloping baths. One of them is developed in a bath C, containing asdeveloping agent only hydroquinone and having the following composition:

Boric acid g Borax g Sodium hexametaphosphate g 1 Sodium sulfite g-Hydroquinone g 4.4

Water up to 1000 cm.

The other film strips are respectively developed in developing bathshaving the same composition as bath C, but containing moreover anequivalent amount of a developing agent as listed in Table III givenhereinafter.

TABLE III Density (D) Time of development 2 4 0 s 10 mm. mm. mm. mm min.

BathC 0.04 0.04 0.04 0.04 0.04 Bath C+53 mg. of p-monomethyl aminophenolhemisulphate 0.04 0.04 0.08 0.18 0.32 Bath O+61 mg. of1-(4-hydroxyphenyl)-pyrrolidine hydrochloride... 0.21 0.99 1.82 BathC+62 mg. of l-(3-chloro-4- hydroxyphenyl)-pyrrolidine 0.74 2.20 BathC+71 mg. 0f1-(2-hydroxyethyD- line hydrochloride 0.22 1.07 1.89 BathC+95 mg. ofl-(rnethylsulfonylaminoethyD-G-hydroxy-l,2,3,4-tetrahydroquinolinehydrochloride 0.24 1.11 1.88 Bath O+60 mg. of l-(3,5,dimethyl-4-hydroxyphenyl)-pyrrolidine 0.14 0.41 0.70 0.98 1.25

Example 4 A light-sensitive material for the silver complex diffusiontransfer process is prepared by coating onto a paper support a gelatinosilverchloro-iodide emulsion (0.5% of iodide). i1 kg. of flowableemulsion has been prepared starting from 45 g. of silver nitrate. Theemulsion is sensitized for light of 500 to 570 m wavelength and is castin such a Way that the silver content amounts to 1.5 g./sq. m. of paper.

The image-receiving material is prepared as follows:

A paper support is coated with an image-receiving layer from asuspension consisting of:

Water cm. 274

Gelatin g 10 Sodium thiosulfate g 12 Sodium sulfide mol 7.7 -10'Cobaltous nitrate =6 aq. mol 1.l l0 1% solution of 1-phenyl-5-mercapto1,2,3,-4-

tetrazole in ethanol cm. 1

so that 13 sq. m. of paper can be coated with 1 1. After drying, thislayer is coated in its turn with a layer from a solution consisting of:

t. Cm. 4% aqueous carboxymethylcellulose 45 Water 155 Sandozol(trademark for a sulfonated organic oil marketed by Sandoz, A. G.,Basel, S\vitzerland) 0.6

The image-receiving material obtained, in close contact with the silverhalide emulsion layer of the lightsensitive material which has beenexposed to a line original, is carried through a developing apparatuscontaining the following composition:

Water cm. 1000 Sodium sulfite g 75 Sodium hydroxide g '10 Potassiumbromide g '1 Hydroquinone g 16 1-(4-hydroxyphenyl)-pyyrolidinehydrochloride I After squeezing the image-receiving layer and thelightsensitive layer between the rubber rollers of the developingapparatus, the image-receiving material and the lightsensitive materialare separated from each other after 10 to 20 seconds of contact and astrong positive image of the original is obtained in the receivinglayer.

Example 5 A light-sensitive material for the silver complex diffusiontransfer process, is prepared by coating onto a paper support of 90g./sq. m. a gelatino silver chloride emulsion containing per litre 0.126mol of silver chloride, 50 g. of gelatin, 2 cm. of a 40% aqueoussolution of saponine and 2 cm. of a 40% aqueous solution offormaldehyde.

The emulsion is coated in such a Way that l g. of silver is applied persq. In.

An image-receiving material is prepared by coating onto a paper supportof 90 g./sq. m., a thin layer from a suspension of the followingcomposition:

Water cm. 837 Gelatin g 40 Sodium thi-osulfate 5 aq g 48 10% aqueoussolution of sodium sulfide cm. 2.5 10% aqueous solution of cobaltnitrate cm. .13 I-lydroquinone g" 6.5 Potassium metabisul fite g 12.8 5%solution of 1-(4-hydroxypheny1)-pyrrolidine in ethanol cm. 40

This suspension is coated in such a way that with 1 litre, 12 sq. m. ofthe support are covered.

The light-sensitive material is now image-wise exposed and together withthe image-receiving material passed through a diffusion transferdeveloping apparatus containing a solution of the following composition:

Water cm. 1000 Trisodium phosphate g 100 Sodium sulfite (anhydrous) g 20In the preparation of a light-sensitive material for the silver complexdiffusion transfer process, a gelatino silver chloride emulsion iscoated onto a paper support of g./sq. m. in such a way that 1 g. ofsilver and 0.1 g. of 1-(4-hydroxyphenyl)pyrrolidine are present per sq.m.

An image-receiving material is prepared by coating onto a SllS- Watercm. 877.2 Gelatin g 40 10% aqueous solution of sodium sulfide cm. 2.410% aqueous solution of cobalt nitrate cm. 13.2 Potassium metabisulfiteg 12.8 Hydroquinone g 6.4 Sodium thiosulfate aq. g 48 This suspension iscoated in such a way that with 1 litre 12 sq. m. of the support arecovered.

The light-sensitive material is now image-wise exposed and together withthe image-receiving material passed through a diflusion transferdeveloping apparatus containing a solution of the following composition:

Water cm. 1000 Trisodium phosphate g 100 Sodium sulfite (anhydrous) g 20After squeezing between the rubber rollers of the developing apparatusand after seconds of contact both materials are separated from eachother.

A positive print of the original is apparent in the imagereceivingmaterial.

What is claimed is:

1. Photographic developing method comprising developing an exposedsilver halide emulsion layer of a photographic material withhydroquinone and a derivative of p-aminophenol having one of thefollowing general formulae:

wherein: 1

R is a member selected from the group consisting of a hydrogen atom anda lower alkyl radical, each of X and X is a member selected from thegroup consisting of a hydrogen atom, a halogen atom, an alkyl group, analkoxy group, an alkyl amido group and an alkyl sulfonamido group,wherein alkyl is lower alkyl, and A is -(CH where n is an integer of 23and A is a propylene radical. 2. Photographic developing solution fordeveloping an exposed silver halide emulsion layer of a photographicmaterial comprising in addition. to. hydroquinone a derivative 1 2 ofp-aminophenol having one of the following general formulae:

I. HZC(IJH2 Hz0\ /CH: N

II. A)- R1I\T g III. -(A') ,.(A')- a K 5 wherein:

R is a member selected from the group consisting of a hydrogen atom anda lower alkyl radical, each of X and X is a member selected from thegroup consisting of a hydrogen atom, a halogen atom, an alkyl group, analkoxy group, an alkyl amido group and an alkyl sulfonamido group,wherein alkyl is lower alkyl, and A is (CH where n is an integer of 2-3and A is a propylene radical.

3. Photographic developing solution according to claim 2 containing from5 to 20 g. of hydroquinone and from 50 mg. to 2 g, of said p-aminophenolderivative.

4. Photographic image-receiving material for use in the silver complexdiffusion transfer process containing in addition to hydroquinone aderivative of p-aminophenol having one of the following generalformulae:

III.

13 wherein:

R is a member selected from the group consisting of a hydrogen atom anda lower alkyl radical,

each of X and X is a member selected from the group consisting of ahydrogen atom, a halogen atom, an alkyl group, an .alkoxy group, analkyl amido group and an alkyl suilfonamido group, wherein alkyl islower alkyl, and

A is -(CH where n is an integer of 2-3 and A is a propylene iradical.

5. Photographic image-receiving material according to claim 4 containingin its image-receiving layer from 0.2 to 20 g. of hydroquinone and from20 mg. to 2 g. of said p-aminophenol derivative per sq. m.

6. Photographic light-sensitive material having a lightsensitivesilver-halide emulsion layer and containing a p-aminophenol derivativehaving one of the following general formulae:

R is a member selected from the group consisting of a hydrogen atom anda lower alkyl radical,

each of X and X is a member selected from the group consisting of ahydrogen atom, a halogen atom, an alkyl group, an .alkoxy group, analkyl amido group and an alkyl suil-fonamido group, wherein alkyl islower alkyl, and

A is -(CH where n is an integer of 2-3 and A is a propylene radical.

7. In a photographic copying method of the diffusion transfer type whichincludes the steps of image-wise exposing a supported silver halideemulsion layer, and developing said exposed layer while in intimatecontact with a supported receiving layer providing development nuclei,

the improvement which comprises carrying out said developing step in thepresence of a super additive combination of developing agents com-prisedessentially of hydroquinone and a derivative of p-aminophenol having oneof the following general formulae: I. Hz(|JCH2 H20 /CH2 11. A)- Rr EIII. em- ,(A)\

wherein:

R is a member selected from the group consisting of a hydrogen atom anda lower alkyl radical,

each of X and X is a member selected from the group consisting of ahydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylamido group and an alkyl sulfonamido group, wherein alkyl is loweralkyl, and

A is (CH where n is an integer of 2-3 and A is a propylene radical.

8. A photographic copying method according to claim 7 wherein thedeveloping step is performed using an alkaline developing solution.

9. The material of claim 6 including, in addition to saidlight-sensitive emulsion layer, a water-permeable layer free oflight-sensitive emulsion in effective contact with said emulsion layer,at least one of said layers containing said p-amino phenol derivative.

References Cited by the Examiner UNITED STATES PATENTS 3,072,480 1/1963Abbott et al. 96-29 OTHER REFERENCES Willems et al.: PhotographicScience and Engineering vol. 6, No. 1, pp. 49-54, January-February 1962.

NORMAN G. TORCHIN, Primary Examiner.

I. T. BROWN, Assistant Examiner.

7. IN A PHOTOGRAPHIC COPYING METHOD OF THE DIFFUSION TRANSFER TYPE WHICH INCLUDES THE STEPS OF IMAGE-WISE EXPOSING A SUPPORTED SILVER HALIDE EMULSION LAYER, AND DEVELOPING SAID EXPOSED LAYER WHILE IN INTIMATE CONTACT WITH A SUPPORTED RECEIVING LAYER PROVIDING DEVELOPMENT NUCLEI, THE IMPROVEMENT WHICH COMPRISES CARRYING OUT SAID DEVELOPING STEP IN THE PRESENCE OF A SUPER ADDITIVE COMBINATION OF DEVELOPING AGENTS COMPRISED ESSENTIALLY OF HYDROQUINONE AND A DERIVATIVE OF P-AMINOPHENOL HAVING ONE OF THE FOLLOWING GENERAL FORMULAE: 